US3247167A - Organo-tin polyamides - Google Patents

Organo-tin polyamides Download PDF

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US3247167A
US3247167A US211110A US21111062A US3247167A US 3247167 A US3247167 A US 3247167A US 211110 A US211110 A US 211110A US 21111062 A US21111062 A US 21111062A US 3247167 A US3247167 A US 3247167A
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tin
diamine
mole
organo
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Emil F Jason
Ellis K Fields
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Standard Oil Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/12—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing tin

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  • This invention relates to synthetic polymeric organotin compositions and to a method of making the same. More particularly, it relates to tin-containing polyamides.
  • the polymeric organo-tin compositions of this invention can be generally designated as the condensation products of a diamine, an organo-tin compound and a dicarboxylic acid. More particularly, the tin-containing 3,247,167 Patented Apr. 19, 1966
  • the dicarboxylic acid reactant is an acyl halide represented by the formula wherein R is an alkylene radical having from 2 to about 20 carbon atoms
  • the phenylene radical and the naphthylpolyamides of this invention are the condensation prodnets of a diamine and a mixture of a diorgano-tin dihalide and an acyl halide of a dicarboxylic acid of the group consisting of alkanedioic acids having from 2 to carbon atoms, benzene dicarboxylic acids and naphthalene dicarboxylic acids, which mixture contains from 1 to 99 mole percent, preferably 5 to 20 mole percent of the diorgano-tin dihalide.
  • the tin-containing polyamides of this invention are linear polymers with a small amount of cross-linking wherein tin is an integral part of, and randomly distributed in, the main polymer chain. These compositions exhibit good thermal stability and fire retarding properties and are suitable for use as stabilizers in polyvinyl chloride plastics, as wood preservatives, in the treatment of textiles for imparting insect resistancy and fire retardancy properties thereto, and as surface coatings.
  • the diamine reactant used in preparing the tin-containing polyamides of this invention are primary amines represented by the formula wherein R is a divalent alkylene, cycloalkylene, arylene, aralkylene or heterocyclic radical. Such radicals can be unsubstituted or contain unreactive, such as alkyl or aryl, substituents.
  • the diamines which are most suitable are the alpha-omega alkylene diamines containing 4 to 22 carbon atoms, which include tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 1,12-dodecadiamine, etc.
  • alkylene diamines are straight or branched chain
  • cycloalkane diamines such as 1,4-cyclohexane diamine
  • Illustrative of the aralkylene diamines are para-amino benzyl amine, para-amino phenethyl amine.
  • the arylene diamines are represented by naphthalene diamine, phenylene diamine.
  • the heterocyclic diamines are those compounds containing nitrogen in the cyclic structure, such as 2,6-diamine pyridine.
  • the diorgano-tin compound used in preparing the compositions of this invention are the diorgano-tin dihalides represented by the formula where R is a C monovalent radical of the group consisting of alkyl and aryl, and X represents halogen, preferably chlorine and bromine.
  • Illustrative organo-tin compounds are dimethyltin dichloride, ethylmethyltin dichloride, diphenyltin dichloride, isopropyl-Z-naphthyltin dichloride, dinaphthyltin dibromide, and dialkyltin dichlorides containing from about 1 to about 20 carbon atoms in each alkyl group.
  • ene radical and X represents a halogen, preferably chlorine or bromine.
  • alkanedioic acids are succinic, adipic and sebacic.
  • the benzene dicarboxylic acids are phthalic, isophthalic and terephthalic acids.
  • representative of the naphthalene dicarboxylic acids are 1,8-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and 2,7-naphthalene dicarboxylic acid.
  • the polymeric organo-tin compositions of this invention are prepared by reacting (A) a diamine and (B) a mixture of a diorgano-tindihalide and an acyl halide from a dicarboxylic acid of the group consisting of alkanedioic acids having from about 2 to 20 carbon atoms, benzene dicarboxylic acids and naphthalene dicarboxylic acids, which mixtures contain from 1 to 99 mole percent of diorgano-tin dihalide in the presence of an aqueous alkali metal hydroxide solution.
  • the alkali metal hydroxide can be sodium hydroxide, potassium hydroxide, lithium hydroxide, with sodium hydroxide being preferred.
  • the alkali metal hydroxide solution contains at least one mole of alkali metal hydroxide per gram atom of halide present in the reaction mixture.
  • Reactants A and B above are preferably in equimolar proportions. However, an excess of either reactant is possible when additional reaction sites are desired in the reaction product obtained in accordance with this invention.
  • the interfacial condensation polymerization of this invention is preferably conducted by dissolving the diamine in the aqueous alkali metal hydroxide solution and thereafter adding a mixture of the diorgano-tin dihalide and acyl halide dissolved in an inert organic solvent such as chloroform to the vigorously agitated aqueous diamine alkali metal hydroxide solution at temperatures within the range of from about 0 to about 200 C., preferably 20 to 30 C., and from atmospheric pressure to superatmospheric pressures of up to about 500 pounds per square inch. At temperatures above 100 C., the reaction should be conducted at super-atmospheric pressures to prevent the loss of water from the reaction medium. The use of elevated temperatures is dependent upon the stability of the reactants.
  • the solvent solution of mixture B is within the range of 5 to by weight of the reactants and preferably 15 to 30% by weight.
  • the aqueous alkali hydroxide solution preferably contains 5 to 20% by weight of the alkaline metal hydroxide and 5 to 40% by weight of the diamine.
  • Recovery of the polymeric organo-tin compositions is simply effected by filtering the solids from the reaction mixture. The solids are then washed with water and dried.
  • Example I A mixture of 11.6 g. (0.1 mole) of 1,6-hexanediamine, 8.0 g. (0.20 mole) of sodium hydroxide, and 100 ml. of water was placed at room temperature in a Waring Blendor. To this stirred solution was added a mixture of 4.2 g. (.019 mole) of dimethyltin dichloride, 16.4 g. (0.082 mole) of terephthaloyl chloride in 200 ml. of chloroform. On addition of the organic solution, a heavy fibrous-like product formed. Filtration and drying of the product gave a colorless solid that is stable up to 350 C. at which temperature it slowly decomposed and analyzed 24% tin by emission spectroscopy.
  • Example II A solution of 5.8 g. (0.05 mole) of 1,6hexanediamine and 4.0 g. (0.1 mole) of sodium hydroxide in 50 ml. of water was prepared. To this stirred solution was slowly added a mixture of 7.3 g. (0.04 mole) of adipoyl chloride and 2.1 g. (0.01 mole) of dimethyltin dichloride in 100 ml. of chloroform. The polymeric composition obtained after filtration and drying decomposed at 250 C., and contained 20% tin by emission spectroscopy measurements.
  • Example III A solution of 2.9 g. (0.02 mole) of 1,6-hexanediamine and 4.0 g. (0.7 mole) of sodium hydroxide in 100 ml. of water was placed in a Waring Blendor. To this stirred solution was added a mixture of 0.9 g. (0.002 mole) of diphenyltin dichloride, and 3.6 g. (0.02 mole) of adipoyl chloride in 100 ml. of chloroform. The solids were removed by filtration, washed several times with Water and dried. The dry material contained 9.76% tin by emission spectroscopy measurements and softened at 250 C., partially sublimed and melted with decomposition at 265-275 C.
  • a portion of the polymeric composition of this example was dissolved in hot dimethylformamide to about a 1% solution.
  • a film on tin plate was cast from this solution. The film exhibited excellent adherence and resisted cracking when the tin plate was bent.
  • Samples of the polymeric compositions of Examples I and II were ignited in a Bunsen flame and found to be self-extinguishing when removed from the flame.
  • polymeric organo-tin compositions of this invention are primarily linear tin-containing polyamides having the following groups 7 randomly distributed throughout the backbone of the composition,
  • Filmand fiber-forming polyamide compositions containing tin in the polymer chain consisting essentially of the condensation product obtained by reacting under polymerizing conditions at least substantially equimolar proportions of (A) a primary diamine having the formula H NR-NH wherein R is a divalent radical containing 4 to 22 carbon atoms selected from the group consisting of alkylene, cycloalkylene, arylene, aralkylene and heterocyclic containing nitrogen in the cyclic structure, and (B) a mixture of (a) a diorganotin dihalide having the formula wherein X is halogen, and R is a monovalent radical containing 1 to 20 carbon atoms selected from the group consisting of alkyl and aryl, and (b) an acyl halide of a dicarboxylic acid from the group consisting of alkanedioic acids having from 2 to about 20 carbon atoms, :benzene dicarboxylic
  • composition of claim 1 wherein said diamine is 1,6-hexanediamine, said tin dihalide is dimethyltin dichloride, said acyl halide is adipoyl chloride, and said alkali metal hydroxide is sodium hydroxide.
  • composition of claim 3 wherein said diamine is 1,6-hexanediamine, said tin dihalide is dimethyltin dichloride, said acyl halide is terephthaloyl chloride, and said alkali metal hydroxide is sodium hydroxide.
  • composition of claim 1 wherein said diamine is 1,6-hexanediamine, said tin dihalide is diphenyltin dichloride, said acyl halide is adipoyl chloride, and said alkali metal hydroxide is sodium hydroxide.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)

Description

United StatesfPatent @iiiice 3,247,167 ORGANO-TIN POLYAMIDES lEmil F. Jason and Ellis K. Fields, Chicago, Ill., assignors to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing. Filed July 19, 1962, Ser. No. 211,110
4 Claims. (Cl. 26078) This invention relates to synthetic polymeric organotin compositions and to a method of making the same. More particularly, it relates to tin-containing polyamides.
The polymeric organo-tin compositions of this invention can be generally designated as the condensation products of a diamine, an organo-tin compound and a dicarboxylic acid. More particularly, the tin-containing 3,247,167 Patented Apr. 19, 1966 The dicarboxylic acid reactant is an acyl halide represented by the formula wherein R is an alkylene radical having from 2 to about 20 carbon atoms, the phenylene radical and the naphthylpolyamides of this invention are the condensation prodnets of a diamine and a mixture of a diorgano-tin dihalide and an acyl halide of a dicarboxylic acid of the group consisting of alkanedioic acids having from 2 to carbon atoms, benzene dicarboxylic acids and naphthalene dicarboxylic acids, which mixture contains from 1 to 99 mole percent, preferably 5 to 20 mole percent of the diorgano-tin dihalide.
The tin-containing polyamides of this invention are linear polymers with a small amount of cross-linking wherein tin is an integral part of, and randomly distributed in, the main polymer chain. These compositions exhibit good thermal stability and fire retarding properties and are suitable for use as stabilizers in polyvinyl chloride plastics, as wood preservatives, in the treatment of textiles for imparting insect resistancy and fire retardancy properties thereto, and as surface coatings.
The diamine reactant used in preparing the tin-containing polyamides of this invention are primary amines represented by the formula wherein R is a divalent alkylene, cycloalkylene, arylene, aralkylene or heterocyclic radical. Such radicals can be unsubstituted or contain unreactive, such as alkyl or aryl, substituents. The diamines which are most suitable are the alpha-omega alkylene diamines containing 4 to 22 carbon atoms, which include tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 1,12-dodecadiamine, etc. While the preferred alkylene diamines are straight or branched chain, cycloalkane diamines such as 1,4-cyclohexane diamine can be used. Illustrative of the aralkylene diamines are para-amino benzyl amine, para-amino phenethyl amine. The arylene diamines are represented by naphthalene diamine, phenylene diamine. The heterocyclic diamines are those compounds containing nitrogen in the cyclic structure, such as 2,6-diamine pyridine.
The diorgano-tin compound used in preparing the compositions of this invention are the diorgano-tin dihalides represented by the formula where R is a C monovalent radical of the group consisting of alkyl and aryl, and X represents halogen, preferably chlorine and bromine. Illustrative organo-tin compounds are dimethyltin dichloride, ethylmethyltin dichloride, diphenyltin dichloride, isopropyl-Z-naphthyltin dichloride, dinaphthyltin dibromide, and dialkyltin dichlorides containing from about 1 to about 20 carbon atoms in each alkyl group.
ene radical; and X represents a halogen, preferably chlorine or bromine. Exemplary of the alkanedioic acids are succinic, adipic and sebacic. The benzene dicarboxylic acids are phthalic, isophthalic and terephthalic acids. representative of the naphthalene dicarboxylic acids are 1,8-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and 2,7-naphthalene dicarboxylic acid.
The polymeric organo-tin compositions of this invention are prepared by reacting (A) a diamine and (B) a mixture of a diorgano-tindihalide and an acyl halide from a dicarboxylic acid of the group consisting of alkanedioic acids having from about 2 to 20 carbon atoms, benzene dicarboxylic acids and naphthalene dicarboxylic acids, which mixtures contain from 1 to 99 mole percent of diorgano-tin dihalide in the presence of an aqueous alkali metal hydroxide solution. The alkali metal hydroxide can be sodium hydroxide, potassium hydroxide, lithium hydroxide, with sodium hydroxide being preferred. Inasmuch as this is an interfacial condensation in an aqueous solution with the elimination of halogen from the reactants, the alkali metal hydroxide solution contains at least one mole of alkali metal hydroxide per gram atom of halide present in the reaction mixture. Reactants A and B above are preferably in equimolar proportions. However, an excess of either reactant is possible when additional reaction sites are desired in the reaction product obtained in accordance with this invention.
The interfacial condensation polymerization of this invention is preferably conducted by dissolving the diamine in the aqueous alkali metal hydroxide solution and thereafter adding a mixture of the diorgano-tin dihalide and acyl halide dissolved in an inert organic solvent such as chloroform to the vigorously agitated aqueous diamine alkali metal hydroxide solution at temperatures within the range of from about 0 to about 200 C., preferably 20 to 30 C., and from atmospheric pressure to superatmospheric pressures of up to about 500 pounds per square inch. At temperatures above 100 C., the reaction should be conducted at super-atmospheric pressures to prevent the loss of water from the reaction medium. The use of elevated temperatures is dependent upon the stability of the reactants. Temperatures below 20 C. reduce the rate of reaction. At room temperature or temperatures within the range of 20 to 30 C., there is maximum reactivity of the reactants with minimal side reactions. The tin-containing polyamide condensation products form immediately as solid materials upon the addition of the dior-gano-tin dihalide and acyl halide mixture to the aqueous diamine alkali metal hydroxide solutions. Consequently, it is advisable to slowly add the diorgano-tin dihalide-acyl halide mixture to the aqueous solution. This polycondensation reaction can be effected by simply admixing the reactants in a high-speed blender, such as a Waring Blendor. Preferentially the solvent solution of mixture B is within the range of 5 to by weight of the reactants and preferably 15 to 30% by weight. The aqueous alkali hydroxide solution preferably contains 5 to 20% by weight of the alkaline metal hydroxide and 5 to 40% by weight of the diamine.
Recovery of the polymeric organo-tin compositions is simply effected by filtering the solids from the reaction mixture. The solids are then washed with water and dried.
The following examples further illustrate the preparation of the tin-containing polyamides of this invention.
Example I A mixture of 11.6 g. (0.1 mole) of 1,6-hexanediamine, 8.0 g. (0.20 mole) of sodium hydroxide, and 100 ml. of water was placed at room temperature in a Waring Blendor. To this stirred solution was added a mixture of 4.2 g. (.019 mole) of dimethyltin dichloride, 16.4 g. (0.082 mole) of terephthaloyl chloride in 200 ml. of chloroform. On addition of the organic solution, a heavy fibrous-like product formed. Filtration and drying of the product gave a colorless solid that is stable up to 350 C. at which temperature it slowly decomposed and analyzed 24% tin by emission spectroscopy.
Example II A solution of 5.8 g. (0.05 mole) of 1,6hexanediamine and 4.0 g. (0.1 mole) of sodium hydroxide in 50 ml. of water was prepared. To this stirred solution was slowly added a mixture of 7.3 g. (0.04 mole) of adipoyl chloride and 2.1 g. (0.01 mole) of dimethyltin dichloride in 100 ml. of chloroform. The polymeric composition obtained after filtration and drying decomposed at 250 C., and contained 20% tin by emission spectroscopy measurements.
Example III A solution of 2.9 g. (0.02 mole) of 1,6-hexanediamine and 4.0 g. (0.7 mole) of sodium hydroxide in 100 ml. of water was placed in a Waring Blendor. To this stirred solution was added a mixture of 0.9 g. (0.002 mole) of diphenyltin dichloride, and 3.6 g. (0.02 mole) of adipoyl chloride in 100 ml. of chloroform. The solids were removed by filtration, washed several times with Water and dried. The dry material contained 9.76% tin by emission spectroscopy measurements and softened at 250 C., partially sublimed and melted with decomposition at 265-275 C.
A portion of the polymeric composition of this example was dissolved in hot dimethylformamide to about a 1% solution. A film on tin plate was cast from this solution. The film exhibited excellent adherence and resisted cracking when the tin plate was bent.
Samples of the polymeric compositions of Examples I and II were ignited in a Bunsen flame and found to be self-extinguishing when removed from the flame.
It will be apparent to one skilled in the art that the polymeric organo-tin compositions of this invention are primarily linear tin-containing polyamides having the following groups 7 randomly distributed throughout the backbone of the composition,
Thus, having described the invention, what is claimed is: 1. Filmand fiber-forming polyamide compositions containing tin in the polymer chain consisting essentially of the condensation product obtained by reacting under polymerizing conditions at least substantially equimolar proportions of (A) a primary diamine having the formula H NR-NH wherein R is a divalent radical containing 4 to 22 carbon atoms selected from the group consisting of alkylene, cycloalkylene, arylene, aralkylene and heterocyclic containing nitrogen in the cyclic structure, and (B) a mixture of (a) a diorganotin dihalide having the formula wherein X is halogen, and R is a monovalent radical containing 1 to 20 carbon atoms selected from the group consisting of alkyl and aryl, and (b) an acyl halide of a dicarboxylic acid from the group consisting of alkanedioic acids having from 2 to about 20 carbon atoms, :benzene dicarboxylic acids and naphthalene dicarboxylic acids, said mixture (B) containing from 1 to 99 mole percent of said diorganotin dihalide, in an aqueous alkali metal hydroxide solution containing at least 1 mole of alkali metal hydroxide per gram atom of halide present in said reaction rnixture (B).
2. The composition of claim 1 wherein said diamine is 1,6-hexanediamine, said tin dihalide is dimethyltin dichloride, said acyl halide is adipoyl chloride, and said alkali metal hydroxide is sodium hydroxide.
3. The composition of claim 1 wherein said diamine is 1,6-hexanediamine, said tin dihalide is dimethyltin dichloride, said acyl halide is terephthaloyl chloride, and said alkali metal hydroxide is sodium hydroxide.
4. The composition of claim 1 wherein said diamine is 1,6-hexanediamine, said tin dihalide is diphenyltin dichloride, said acyl halide is adipoyl chloride, and said alkali metal hydroxide is sodium hydroxide.
References Cited by the Examiner UNITED STATES PATENTS 2,625,536 1/1953 Kirby 26078 2,722,524 11/1955 Speck 26078 2,831,834 4/1958 Magat 26078 2,918,454 12/1959 Graham 26078 2,924,586 2/1960 Lotz et a1. 26078 3,067,168 12/1962 Purdon 26078 FOREIGN PATENTS 1,253,028 12/1960 France.
WILLIAM H. SHORT, Primary Examiner.
JOSEPH R. LIBERMAN, Examiner,

Claims (1)

1. FILM- AND FIBER-FORMING POLYAMIDE COMPOSITIONS CONTAINING TIN IN THE POLYMER CHAIN CONSISTING ESSENTIALLY OF THE CONDENSATION PRODUCT OBTAINED BY REACTING UNDER POLYMERIZING CONDITIONS AT LEAST SUBSTANTIALLY EQUIMOLAR PROPORTIONS OF (A) A PRIMARY DIAMINE HAVING THE FORMULA
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3485803A (en) * 1964-10-01 1969-12-23 Centre Nat Rech Scient Organometallic polyamides
US3640747A (en) * 1968-09-12 1972-02-08 Polymer Corp Method of reducing sandiness in vinyl coatings

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2625536A (en) * 1951-05-05 1953-01-13 Du Pont Neutral esters of dicarboxylic acid orthophosphoric acid mixed anhydrides and condensation polymerization process utilizing the same
US2722524A (en) * 1951-09-24 1955-11-01 Du Pont Synthetic linear condensation polymers containing silicon
US2831834A (en) * 1951-05-12 1958-04-22 Du Pont Process for preparing polyamides
US2918454A (en) * 1954-08-16 1959-12-22 Ethyl Corp Condensation polymers
US2924586A (en) * 1956-06-16 1960-02-09 Glanzstoff Ag Process for the refining of synthetic linear polymerizates or polycondensates
FR1253028A (en) * 1959-05-04 1961-02-03 Union Carbide Corp Process for stabilizing polyamides by incorporating organic tin compounds
US3067168A (en) * 1960-05-13 1962-12-04 Du Pont Synthetic polyamides stabilized with thermally stable ionic tin salts

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2625536A (en) * 1951-05-05 1953-01-13 Du Pont Neutral esters of dicarboxylic acid orthophosphoric acid mixed anhydrides and condensation polymerization process utilizing the same
US2831834A (en) * 1951-05-12 1958-04-22 Du Pont Process for preparing polyamides
US2722524A (en) * 1951-09-24 1955-11-01 Du Pont Synthetic linear condensation polymers containing silicon
US2918454A (en) * 1954-08-16 1959-12-22 Ethyl Corp Condensation polymers
US2924586A (en) * 1956-06-16 1960-02-09 Glanzstoff Ag Process for the refining of synthetic linear polymerizates or polycondensates
FR1253028A (en) * 1959-05-04 1961-02-03 Union Carbide Corp Process for stabilizing polyamides by incorporating organic tin compounds
US3067168A (en) * 1960-05-13 1962-12-04 Du Pont Synthetic polyamides stabilized with thermally stable ionic tin salts

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3485803A (en) * 1964-10-01 1969-12-23 Centre Nat Rech Scient Organometallic polyamides
US3640747A (en) * 1968-09-12 1972-02-08 Polymer Corp Method of reducing sandiness in vinyl coatings

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